Poly-1-n-alkenylamines, and fuel and lubricant compositions containing them

ABSTRACT

Fuel and lubricant compositions contain a poly-1-n-alkenylamine as an additive.

This application is a 371 of PCT/EP 941/01113, filed Apr. 11, 1994.

The present invention relates to poly-1-n-alkenylamines and fuel andlubricant compositions which contain poly-1-n-alkenylamines.

Polybutenylamines and their use as fuel and lubricant additives havebeen known for a very long time and are described, for example, in U.S.Pat. No. 3 275 554 and DE-A-2 125 039.

The prior art polybutenylamines are prepared by halogenation ofpolybutenes and reaction of the halides with amines. In the preparationof these products, ionic halides are formed and have to be verysubstantially removed.

There has therefore been no lack of attempts in the prior art to improvethe known products, especially since not only does the elimination ofthe ionic halide require expensive measures but also considerableamounts of halogen always remain in the reaction products (cf. DE-A-2245 918).

EP 244 616 B1 discloses polyisobutenylamines which are very useful asfuel and lubricant additives. The polyisobutenes required for thepreparation of these additives are, however, difficult to obtain owingto the fact that the starting material isobutene is available only bymeans of expensive processes.

It is an object of the present invention to provide fuel or lubricantcompositions which prevent deposits in the intake system of gasolineengines, have a particularly good dispersant effect and furthermore aretechnically readily obtainable.

We have found that this object is achieved by a fuel or lubricantcomposition which contains at least one poly-1-n-alkenylamine of theformula I ##STR1## where R₁ is a poly-1-n-alkene radical derived fromone or more 1-n-alkenes of 3-6 carbon atoms and 0-50% by weight ofethene and R₂ and R₃ may be identical or different and are eachhydrogen, aliphatic or aromatic hydrocarbons, primary or secondary,aromatic or aliphatic aminoalkylene radicals or polyaminoalkyleneradicals, polyoxyalkylene radicals, heteroaryl or heterocycyl radicalsor, together with the nitrogen atom to which they are bonded, form aring in which further hetero atoms may be present.

A preferred embodiment of the invention provides a fuel or lubricantcomposition containing at least one poly-1-n-alkenylamine of the formulaI, where R₁ has the is abovementioned meanings and R₂ and R₃ areidentical or different and are each hydrogen, alkyl, aryl,hydroxy-alkyl, an aminoalkylene radical of the formula II ##STR2## whereR₄ is an alkylene radical and R₅ and R₆ are identical or different andare each hydrogen, alkyl, aryl or hydroxyalkyl, or a polyaminoalkyleneradical of the formula III ##STR3## where radicals R₄ are identical ordifferent and the radicals R₅ are identical or different and R₄, R₅ andR₆ have the abovementioned meanings and m is an integer of from 1 to 7,or a polyalkylene radical of the formula IV ##STR4## where the radicalsR₄ may be identical or different and have the abovementioned meanings, Xis C₁ -C₆ -alkyl or H and n is an integer from 1 to 30, or where R₂ andR₃, together with the nitrogen atom to which they are bonded, form amorpholinyl, pyridyl, piperidyl, pyrrolyl, pyrimidinyl, pyrrolinyl,pyrrolidinyl, pyrazinyl or pyridazinyl radical.

A particularly preferred embodiment provides a fuel or lubricantcomposition containing at least one poly-1-n-alkenylamine of the formulaI ##STR5## where R₁ is a poly-1-alkene radical of 20 to 400 carbon atomswhich is derived from one or more 1-n-alkenes of 3-6 carbon atoms and0-50% by weight of ethene and R₂ and R₃ are identical or different andare each hydrogen, C₁ -C₁₀ -alkyl, phenyl, naphthyl, C₁ -C₁₀-hydroxyalkyl, an aminoalkylene radical of the formula II ##STR6## whereR₄ is a C₂ -C₁₀ -alkylene radical and R₅ and R₆ are identical ordifferent and are each hydrogen, C₁ -C₁₀ -alkyl, phenyl, naphthyl or C₁-C₁₀ -hydroxy-alkyl, a polyaminoalkylene radical of the formula III##STR7## where the radicals R₄ are identical or different, the radicalsR₅ are identical or different, R₄, R₅ and R₆ have the above meanings andm is an integer from 1 to 7, or a polyoxyalkylene radical of the formulaIV ##STR8## where the radicals R₄ are identical or different and havethe above meanings, X is C₁ -C₆ -alkyl or H and n is an integer of from1 to 30, or where R₂ and R₃ together with the nitrogen atom to whichthey are bonded, form a morpholinyl radical.

A further particularly preferred embodiment provides a fuel or lubricantcomposition containing at least one poly-1-n-alkenylamine of the formulaI, where R₁ is a poly-1-n-alkene radical, in particular of 32 to 200carbon atoms, derived from one or more 1-n-alkenes of 3 or 4 carbonatoms and 0-40% by weight of ethene, and R₂ and R₃ are identical ordifferent and are each hydrogen, methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, phenyl,##STR9## where p is an integer of from 1 to 7, in particular from 1 to3, ##STR10## where q is an integer of from 1 to 30, or, together withthe nitrogen atom to which they are bonded, form a morpholinyl radical.

Particularly advantageous fuel or lubricant compositions are thosecontaining at least one poly-1-n-alkenylamine of the formula I which isobtainable by polymerization of 1-n-alkenes in the presence of ametallocene catalyst of the formula V

    CP.sub.m MX.sub.n Y.sub.r V

where Cp is an unsubstituted or substituted cyclopentadiene ring, M is atransition metal of group 4 b, X is hydrogen or C₁ -C₆ -alkyl, Y ishalogen, m is 1-3, n is 0-3, r is 0-3 and m+n+r corresponds to thevalency of M, subsequent hydroformylation of the poly-1-n-alkene formedand amination of the hydroformylated reaction product underhydrogenating conditions.

Particularly preferred fuel or lubricant compositions are those whichcontain a poly-1-n-alkenylamine I in which R₁ is derived from apolypropylene or an ethene-1-butene copolymer.

Where the present invention relates to a fuel composition, in particulara fuel for internal combustion engines, the poly-1-n-alkenylamine of theformula I may be present, for example, in an amount of 10-5,000, inparticular 100-800, mg/kg of fuel.

The poly-1-n-alkenylamine may be present in the novel lubricantcomposition, for example, in an amount of 0.5-5, in particular 1-3, % byweight, based on the total weight of the composition.

The present invention also relates to poly-1-n-alkenylamines of theformula I ##STR11## where R₁ is a poly-1-n-alkene radical derived fromone or more 1-n-alkenes of 3-6 carbon atoms and 0-50% by weight ofethene, in particular from propene or an ethene/1-butene mixture, and R₂and R₃ are identical or different and are each hydrogen, C₁ -C₁₀ -alkyl,phenyl, naphthyl, C₁ -C₁₀ -hydroxyalkyl, an aminoalkylene radical of theformula II ##STR12## where R₄ is a C₁ -C₁₀ -alkylene radical and R₅ andR6 are identical or different and are each hydrogen, C₁ -C₁₀ -alkyl,phenyl, naphthyl or C₁ -C₁₀ -hydroxyalkyl, a polyaminoalkylene radicalof the formula III ##STR13## where the radicals R₄ are identical ordifferent, the radicals R₅ are identical or different, R₄, R₅ and R₆have the above meanings and m is an integer of from 1 to 7, or apolyoxyalkylene radical of the formula IV ##STR14## where the radicalsR₄ are identical or different and have the above meanings, X is C₁ -C₆-alkyl or H and n is an integer of from 1 to 30, or where R₂ and R₃,together with the nitrogen atom to which they are bonded, form a ring inwhich further hetero atoms may be present.

The present invention finally also relates to the use of thepoly-1-n-alkenylamines of the formula I, where R₁, R₂ and R₃ have theabovementioned meanings, as additives in fuel or lubricant compositions,in particular for internal combustion engines.

The compounds of the formula I can be prepared, for example, by firstpolymerizing a 1-n-alkene in the presence of a metallocene catalyst ofthe formula V

    Cp.sub.m MX.sub.n Y.sub.r V

where Cp is an unsubstituted cyclopentadienyl unit and/or a mono-C₁ -C₄-alkylcyclopentadienyl unit, M is a zirconium or hafnium atom and theligands X are hydride and/or halide ions and/or methyl, and in thepresence of an aluminoxane cocatalyst, employing the catalyst and thealuminoxane cocatalyst in a ratio which corresponds to an M/Al atomicratio of from 1:250 to 1:1000 and using temperatures of from 50° to 110°C. and a pressure of from 30 to 100 bar.

The catalysts V are zirconocenes and hafnocenes and therefore complexesof tetravalent zirconium and hafnium in which the metal atom M is bondedin the form of a sandwich between two unsubstituted and/or C₁ -C₄-monoalkyl-substituted cyclopentadienyl groups Cp, the remainingvalences of the central atom M being saturated by hydride and/or halideions and/or by methyl groups. Zirconocene and hafnocene catalysts whichare particularly preferably used in the novel process are those whosecyclopentadienyl groups are unsubstituted. The halide ions bonded to themetal atom may be fluoride, chloride, bromide and/or iodide anions.

Examples of suitable catalysts are: CP₂ ZrF₂, CP₂ ZrCl₂, CP₂ ZrCl₂, Cp₂ZrI₂, Cp₂ ZrCl, Cp₂ Zr(CH₃)Cl, Cp₂ Zr(CH₃)₂, Cp₂ HfF₂, Cp₂ HfCl₂, Cp₂HfBr₂, CP₂ HfJ₂, CP₂ HfHCl, Cp₂ Hf(CH₃)Cl and Cp₂ Hf(CH₃)₂ .

Advantageously, only one catalyst is used in the oligomerization, but itis also possible to use mixtures of different catalysts. Preferredligands X are chloride, hydride and methyl, and zirconium isparticularly preferred as the central atom M for the catalyst V.Zirconocene chloride of the formula Cp₂ ZrCl₂ whose cyclopentadienylgroups are unsubstituted is particularly preferably used as thecatalyst.

The catalysts can be synthesized in a simple manner by known processes,for example according to Brauer (Editor): Handbuch der Praiparativen,Anorganischen Chemie, Volume 2, 3rd Edition, pages 1395 to 1397, Enke,Stuttgart 1978.

The cocatalysts used are organoaluminum compounds, preferablyaluminoxanes. Aluminoxanes are formed in the partial hydrolysis oforganoaluminum compounds, for example those of the formulae AlR₃, AlR₂ Yand Al₂ R₃ Y₃, in which R may be, for example, C₁ -C₁₀ -alkyl,preferably C₁ -C₅ -alkyl, C₃ -C₁₀ -cycloalkyl, C₇ -C₁₂ -aralkyl oralkylaryl and/or phenyl or naphthyl and Y may be hydrogen, halogen,preferably chlorine or bromine, or C₁ -C₁₀ -alkoxy, preferably methoxyor ethoxy. The partial hydrolysis of such organoaluminum compounds canbe carried out by various processes, for example by the process of DE-A3 240 383 or by that stated in EP-A 268 214. The resultingoxygen-containing aluminoxanes are in general not pure compounds butoligomer mixtures of the formula VI ##STR15## where, as a rule, n isfrom 6 to 20 and R has the above-mentioned meanings. If organoaluminumcompounds having different radicals R or mixtures of organoaluminumcompounds having different radicals R are hydrolysed, aluminoxaneshaving different radicals R are formed and may likewise be used ascocatalysts. However, aluminoxanes are advantageously used ascocatalysts. A preferably used aluminoxane is methylaluminoxane. Since,owing to their method of preparation, the aluminoxanes used ascocatalysts are not pure compounds, the molarity of aluminoxanesolutions is related to their aluminum content below.

For the polymerization, the catalyst and the cocatalyst are used in anamount which corresponds to an M/Al atomic ratio of in general from1:250 to 1:1000, preferably from 1:300 to 1:600, in particular from1:400 to 1:500.

The polymerization of the 1-n-alkene is advantageously carried out inthe liquid phase and in a solvent, advantageously with the use of smallamounts of a solvent, preferably of an aliphatic or aromatichydrocarbon, such as bezene, toluene, xylene, ethylbenzene, cumene,naphthalene, tetralin, hexane, heptane, octane, isooctane, nonane,decane, dodecane, cyclohexane, decalin, petroleum ether or ligroin.Particularly preferably used solvents are toluene and xylene. In thisprocess, solvent/1-n-alkene volume ratios of in general from 1:20 to1:500, preferably from 1:30 to 1:200, particularly preferably from 1:40to 1:100 are established, the volume of the 1-n-alkene relating to itsvolume at the particular pressure applied. The 1-n-alkene is liquidunder the conditions used.

The polymerization is generally carried out at from 50° to 110° C.,particularly preferably at from 60° to 90° C., and at from 30 to 100bar, preferably at from 30 to 50 bar. The metallocene/1-n-alkene ratiois generally not crucial for the process, but is expediently from 1:50to 1:250000, preferably from 1:70 to 1:200000, in particular from 1:90to 1:190000.

The polymerization process can be carried out both batchwise, forexample in stirred autoclaves, or continuously, for example in tubularreactors. After the catalyst has been separated off by distillation ofthe products or by hydrolysis thereof followed by filtration of theprecipitated solids, the reaction mixture is advantageously worked by updistillation, if desired under reduced pressure.

The propene preferably used as a raw material in this process mayoriginate from a variety of sources, for example from crack gases, eg.from steam crack gas. Propene as formed, for example, in propanedehydrogenation may also be used. Propene may be used in purified formbut also as mixtures with other hydrocarbons which are inert under theconditions of the reaction.

The polymerization process permits the selective preparation ofpoly-1-n-alkenes having terminal double bonds, in particular theselective preparation of propene polymers with high productivity.

The poly-1-n-alkenes, in particular the copolymers of ethene and1-n-alkenes, can also be prepared by other known processes, asdescribed, for example, in EP 0441 548 A1. Here too, a metallocenecatalyst is used in combination with an aluminoxane. Cyclopentadienyltransition metal compounds of the formula V are likewise used here asmetallocenes, preferred transition metals being Ti, Zr and Hf.

The poly-1-n-alkenes prepared are distilled if necessary and thenhydroformylated in a conventional manner, using a rhodium or cobaltcatalyst in the presence of CO and H₂ at from 80° to 200° C. and CO/H₂pressures of up to 600 bar.

The reaction product (oxo product) is then aminated under hydrogenatingconditions. The amination reaction is advantageously carried out at80°-200° C. and up to 600, preferably 80-300, bar.

In the hydroformylation and amination reaction, a suitable, inertsolvent is advantageously used in order to reduce the viscosity of thereaction mixture. Suitable solvents are in particular low-sulfuraliphatic, cycloaliphatic and aromatic hydrocarbons. Aliphatic solventswhich are free of sulfur compounds and contain less than 1% of aromaticsare particularly preferred. They have the advantage that no heat ofhydrogenation is evolved at high amination temperatures and no hydrogenis consumed. In the amination and hydroformylation reaction, the solventcontent is from 0 to 70% by weight, depending on the viscosity of thepolymer and of the solvent. Higher dilutions are just as uneconomical asreplacement of the solvent between hydroformylation and amination.

The oxo product formed in the hydroformylation reaction is usuallypresent as an aldehyde/alcohol mixture. It may be further processed as amixture or may be completely hydrogenated beforehand to improve itsshelf life. Completely hydrogenated products are less reactive.

Owing to their preparation, the poly-1-n-alkenylamines used in the novelfuels or lubricants contain no halogen and furthermore have nounsaturated components, making them particularly suitable for use infuels or lubricants.

Owing to their structure, the novel poly-1-n-alkenylamines have both adispersant and a detergent effect. This means that, as detergents, theyhave a keep-clean effect in valves and carburetors or injection systems.When these dispersants enter the lubricant circulation of the engine viathe combustion chamber, they help to improve the dispersing of sludge inengine oil.

If it is intended primarily to utilize the dispersant properties of thepoly-1-n-alkenylamines, they may also be combined with conventionaldetergents as further additives.

In principle, any known products suitable for this purpose may be usedas the detergent component in the mixture containing the novelsubstances as dispersants, such products being described, for example,in J. Falbe and U. Hasserodt, Katalysatoren, Tenside undMineraloladditive, G. Thieme Verlag Stuttgart 1978, page 221 et seq. orin K. Owen, Gasoline and Diesel Fuel Additives, John Wiley & Sons 1989,page 23 et seq.

N-Containing detergents, for example compounds which contain an amino oramido group, are preferably used. Polyisobutylamines according to EP 0244 616, ethylenediaminetetraacetamides and/or -imides according to EP 0188 786 or polyetheramines according to EP 0 244 725 are particularlysuitable, reference being made to the definitions in these publications.As a result of their preparation, the products described there likewisehave the advantage of being chlorine-free and chloride-free.

If it is intended primarily to utilize the detergent effect of the novelcompounds, these substances may also be combined with carrier oils. Suchcarrier oils are known, particularly suitable ones beingpolyglycol-based carrier oils, for example corresponding ethers and/oresters, as described in U.S. Pat. No. 5 004 478 or DE 38 38 918 A1.Polyoxyalkylenemonools having terminal hydrocarbon groups (U.S. Pat. No.4 877 416) or carrier oils as disclosed in DE 41 42 241 A1 may also beused.

Suitable fuels for gasoline engines are leaded and in particularunleaded regular and premium grade gasoline. The gasolines may alsocontain components other than hydrocarbons, for example alcohols, suchas methanol, ethanol or tert-butanol, and ethers, eg. methyl tert-butylether. In addition to the novel poly-1-n-alkenylamines to be usedaccording to the invention, the fuels also contain, as a rule, furtheradditives, such as corrosion inhibitors, stabilizers, antioxidantsand/or further detergents.

Corrosion inhibitors are generally ammonium salts of organic carboxylicacids, which tend to form films owing to the fact that the startingcompounds have the appropriate structure. Amines for reducing the pH arealso frequently present in corrosion inhibitors. Heterocyclic aromaticsare generally used for protecting non-ferrous metals from corrosion.

Testing of the novel poly-1-n-alkenylamines with regard to theirsuitability as valve cleaners is carried out by means of engine testsusing a 1.2 l Opel Kadett engine.

EXAMPLES

1. Preparation of poly-1-n-alkenes 1.1 30 ml of a 1.5 molar solution ofmethylaluminoxane in toluene were initially taken in a 2 1 stirredautoclave, 900 ml (13.3 mol) of liquid propene were condensed therewithand the mixture was heated to 60° C. The resulting pressure was 20 bar.Thereafter, 40.5 mg (0.17 mmol) of zirconocene(dicyclopentadienylzirconium dichloride), dissolved in 7 ml of a 1.5molar solution of methylaluminoxane in toluene, were added andoligomerization was effected in the course of 60 minutes. Thealuminum/zirconium atomic ratio was 250:1. A yield of 590 ml of propeneoligomers was obtained. The productivity of the catalyst under thereaction conditions used, expressed as ml of product per g of catalystper hour, was 11,900. Gas chromatographic analysis of the product gavethe following composition:

    ______________________________________                                        Oligomers      C.sub.6 :                                                                           16.3%                                                                   C.sub.9 :                                                                           24.1%                                                                  C.sub.12 :                                                                           16.5%                                                                  C.sub.15 :                                                                            5.9%                                                                  C.sub.18 :                                                                            2.3%                                                                 ≧C.sub.21 :                                                                    34.9%                                                    ______________________________________                                    

Analysis of the resulting products by infrared and NMR spectroscopyshows that only hydrocarbons having terminal double bonds which arepredominantly localized in vinylidene groups were formed.

Examples 2 to 4 were carried out similarly to Example 1, the variousaluminum/zirconium atomic ratios stated in the Table being used.

    ______________________________________                                                                           Productivity                               Exam- Zirconocene                                                                             Methylalumin-                                                                            Al/Zr atomic                                                                           ml of product                             ple    mmol!    oxane  mmol!                                                                             ratio   per g caat. per h!                         ______________________________________                                        1.2   0.17      90         530     14600                                      1.3   0.07      30         430     18600                                      1.4   0.07      60.5       860     20100                                      ______________________________________                                    

EXAMPLE 1.5

30 ml of a 1.5 molar solution of methylaluminoxane in toluene wereinitially taken in a 1 1 stirred autoclave, 500 ml (6.3 mol) of liquid1-n-butene were condensed therewith and the mixture was heated to 80° C.The resulting pressure was 13 bar. 0.1 mol of ethylene was then meteredin. After the addition of 28 mg (0.096 mmol) of zirconocene,oligomerization was effected for 30 minutes.

551 ml of a butene-ethylene oligomer were isolated.

2. Hydroformylation 2.1 The propene oligomer prepared according toExample 1.1 was distilled and the fraction≧C₂₁ was hydroformylatedwithout a solvent at two different temperatures (120° and 160° C.) at280 bar. Starting material Iodine number: 49 g of iodine/100 g A)High-pressure hydroformylation at 120° C.

A solution of 4.5 g of 85% strength cobalt carbonyl in 700 g ofpolypropene 0.18% of cobalt! was reacted in a 2.5 1 autoclave having alift-type stirrer for 5 hours at 120° C. and a CO/H₂ pressure of 280bar. In order to separate off the cobalt catalyst, the reaction mixturewas let down and then stirred for one hour with the same volume of a 10%strength acetic acid solution at from 90° to 95° C. with passage of air,and the cobalt-containing aqueous phase was separated off.

The oxo product had the following characteristics:

Iodine number: 8.6 g of iodine/100 g

CO number: 67 mg KOH/g

OH number: 1 mg KOH/g

Conversion: 80%

Yield: 85.5% (determined by column chromatography)

B) High-pressure hydroformylation at 160° C. Procedure as for ACharacteristics of oxo product:

Iodine number: 0.1

CO number: 2.5 under acidic conditions at elevated temperatures

CO number: 2.5 under alkaline conditions at room temperature

OH number: 40

Conversion: 99.8% 2.2 The butene-ethylene oligomer prepared according toExample 1.5 was hydroformylated batchwise using cobalt under thefollowing conditions:

The starting material iodine number 53! was used in the form of a 30%strength solution in toluene.

Apparatus: 2.5 1 autoclave with lift-type stirrer

Temperature: 160° C.

Pressure: 260-280 bar CO/H₂ 1:1

Cobalt: 0.18% in the feed

Cobalt as: carbonyl

Time: 5 hours

To separate off the cobalt catalyst, the reaction mixture was let downand then stirred for one hour with the same volume of 10% strengthacetic acid solution at from 90° to 95° C. with passage of air, and thecobalt-containing phase was then separated off. The solvent was thenremoved under reduced pressure.

    ______________________________________                                        % a) %          Iodine                   Acid                                 Yield                                                                              Conversion number  CO number                                                                              OH number                                                                             number                               ______________________________________                                        96   98.7       0.7     15       55      1.2                                  ______________________________________                                         a) Determined by column chromatography                                   

3. Amination 3.1 760 ml of NH₃ (liquid) and 75 g of Raney nickel wereadded to 400 g of the hydroformylation product according to Example 2.1Ain a stirred autoclave, and heating was carried out for 4 hours at 180°C. and at a H₂ pressure of 280 bar. After filtration, the product hadthe following characteristics:

Amine number: 60.5

Secondary and tertiary amine number: 1.6

OH number: 7.7

3.2 300 g of the hydroformylation product according to Example 2.1A wereheated with 40 g of diethylenetriamine, 150 g of cyclohexane and 50 g ofRaney nickel in a stirred autoclave at 180° C. for 4 hours and at a H₂pressure of 280 bar. After filtration and evaporation of the solvent,the residue had the following characteristics:

Amine number: 115.0

Secondary and tertiary amine number:44.6

OH number: 6.1

4. Engine tests

The engine tests were carried out in an Opel Kadett 1.2 1 engine. Thefuel used was European premium grade unleaded fuel.

    ______________________________________                                                      Deposits in intake valves, in mg                                Additive   Dose     Valves  1    2     3    4                                 ______________________________________                                        Polypropyleneamine                                                                       800 ppm          0    0     0    0                                 according to                                                                  Example 3.1                                                                   Base value without additive                                                                           830    384   338  750                                 ______________________________________                                    

This shows that the novel polyalkenylamines have an excellent effect asa detergent.

5. Spot test

A 3% strength by weight mixture of the polypropyleneamine according toExample 3.1 with a dispersion of carbon black in a mineral oil wasprepared by heating to 50° C. for 1 hour. The dispersion thus obtainedwas developed on a filter paper in the same way as a chromatogram. Thearea of pure oil and that of distributed carbon black were compared(description of test: Les Huiles pour Moteurs et le Fraissage desMoteurs, A. Schilling, Vol. 1, page 89 et seq., 1962).

    ______________________________________                                        Additive content of                                                                           Proportionate areas of                                        carbon black dispersion                                                                       carbon black                                                   % by weight!    %9!                                                          ______________________________________                                        0               22                                                            3               45                                                            ______________________________________                                    

The test clearly shows the dispersant properties of the novelpoly-1-n-alkenylamines.

We claim:
 1. A composition, which comprises a fuel and at least onepoly-1-n-alkenylamine of the formula I ##STR16## where R₁ is apoly-1-n-alkene radical derived from one or more 1-n-alkenes of 3-6carbon atoms and 0-50% by weight of ethene andR₂ and R₃ may be identicalor different and are each hydrogen, hydroxyalkyl, aliphatic or aromatichydrocarbons, primary or secondary, aromatic or aliphatic aminoalkyleneradicals or polyaminoalkylene radicals, polyoxyalkylene radicals,heteroaryl or heterocyclyl radicals, or together with the nitrogen atomto which they are bonded, form a ring in which further hetero atoms maybe present, wherein the poly-I-alkenylamine is obtained by a processcomprising a) polymerization of 1 -n-alkene in the presence of ametallocene catalyst of the formula V

    Cp.sub.m MX.sub.n Y.sub.r V

where Cp is an unsubstituted or substituted cyclopentadiene ring, M is atransition metal of group 4 b, X is hydrogen or C₁ -C₆ -alkyl, Y ishalogen, m is 1-3, n is 0-3, r is 0-3 and m+n+r correspond to thevalency of M; b) subsequent hydroformylation of the poly-1-n-alkene; andc) amination of the reaction product from reaction step b) underhydrogenating conditions.
 2. The composition of claim 1, wherein R₂ andR₃ are identical or different and are each hydrogen, alkyl, aryl,hydroxyalkyl, an aminoalkylene radical of the formula II ##STR17## whereR₄ is an alkylene radical andR₅ and R₆ are identical or different andare each hydrogen, alkyl, aryl, hydroxyalkyl, a polyaminoalkyleneradical of the formula III ##STR18## where the radicals R₄ are identicalor different, the radicals R, are identical or different, R₄, R₅ and R₆have the above-mentioned meanings and m is an integer of from 1 to 7, ora polyalkylene radical of the formula IV ##STR19## where the radicals R₄may be identical or different and have the above-mentioned meanings, Xis C₁ -C₆ -alkyl or H and n is an integer from 1 to 30, or where R₂ andR₃, together with the nitrogen atom to which they are bonded, form amorpholinyl, pyridyl, piperidyl, pyrrolyl, pyrimidinyl, pyrrolinyl,pyrrolidinyl, pyrazinyl or pyridazinyl radical.
 3. The composition ofclaim 1, wherein R₁ is a poly-1-n-alkene radical of 20 to 400 carbonatoms which is derived from one or more 1-n-alkenes of 3-6 carbon atomsand 0-50% by weight of ethene andR₂ and R₃ are identical or differentand are each hydrogen, Cl-C,₀ -alkyl, phenyl, naphthyl, C₁ -C₁₀-hydroxyalkyl, an aminoalkylene radical of the formula II ##STR20##where R₄ is a C₂ -C₁₀ -alkylene radical and R₅ and R6 are identical ordifferent and are each hydrogen, Cl-C,O-alkyl, phenyl, naphthyl, C₁ -C₁₀-hydroxyalkyl, a polyaminoalkylene radical of the formula III ##STR21##where the radicals R₄ are identical or different, the radicals R₅ areidentical or different, R₄, R₅ and R₆ have the above-mentioned meaningsand m is an integer of from 1 to 7, or a polyalkylene radical of theformula IV ##STR22## where the radicals R₄ may be identical or differentand have the above-mentioned meanings, X is C₁ -C₆ -alkyl or H and n isan integer from 1 to 30, or where R₂ and R₃, together with the nitrogenatom to which they are bonded, form a morpholinyl radical.
 4. Thecomposition of claim 3, where R₁ is a poly-1-n-alkene radical derivedfrom one or more 1-n-alkenes of 3 or 4 carbon atoms and from 0 to 40% byweight of ethene, and R₂ and R₃ are identical or different and are eachhydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, pentyl, hexyl, phenyl, ##STR23## where p is aninteger from 1 to 7, ##STR24## where q is an integer from 1 to 30, or,together with the nitrogen atom to which they are bonded, form amorpholinyl radical.
 5. The composition of claim 4, wherein p is aninteger of from 1 to
 3. 6. The composition of claim 1, which comprisesat least one poly-1-n-alkenylamine wherein R, is a poly-1-n-alkeneradical derived from propene or from an ethene/1-n-butene mixture. 7.The composition of claim 1, wherein said poly-1-n-alkenylamine ispresent in an amount of from 10 to 5,000 ppm, based on the total weightof said composition.
 8. The composition of claim 7, wherein saidpoly-1-n-alkenylamine is present in an amount of from 100 to 800 ppm,based on the total weight of said composition.
 9. The composition ofclaim 1, wherein said fuel comprises gasoline.
 10. The composition ofclaim 9, wherein said gasoline is leaded gasoline.
 11. The compositionof claim 9, wherein said gasoline is unleaded gasoline.
 12. Thecomposition of claim 9, wherein said gasoline is premium gasoline. 13.The composition of claim 9, wherein said gasoline comprises at least onecomponent selected from the group consisting of methanol, ethanol,tert-butanol, and methyl tert-butyl ether.
 14. A composition, whichcomprises a fuel and at least one poly-1-n-alkenylamine of the formula I##STR25## where R₁ is a poly-1-n-alkene radical derived from propene orfrom an ethene/1-n-butene mixture andR₂ and R₃ may be identical ordifferent and are each hydrogen, hydroxyalkyl, aliphatic or aromatichydrocarbons, primary or secondary, aromatic or aliphatic aminoalkyleneradicals or polyaminoalkylene radicals, polyoxyalkylene radicals,heteroaryl or heterocyclyl radicals, or together with the nitrogen atomto which they are bonded, form a ring in which further hetero atoms maybe present.
 15. The composition of claim 14, wherein said fuel comprisesgasoline.
 16. The composition of claim 15, wherein said gasoline isleaded gasoline.
 17. The composition of claim 15, wherein said gasolineis unleaded gasoline.
 18. The composition of claim 15, wherein saidgasoline is premium gasoline.
 19. The composition of claim 15, whereinsaid gasoline comprises at least one component selected from the groupconsisting of methanol, ethanol, tert-butanol, and methyl tert-butylether.